近日，上海交通大学马佳佳团队报道了具有单配位活性位点的Ir（III）钳形配合物作为半夹心催化剂的替代物：实现不对称酰基硝基转移和结构-活性关系研究。这一研究成果于2025年10月13日发表在《美国化学会志》上。

金属酰基硝基类化合物的不对称C(sp³)-H酰胺化已成为一种获取对映体富集酰胺和手性胺的高效合成策略。虽然最先进的过渡金属催化剂通常具有半三明治支架，但人们对新型催化剂支架的探索仍颇感兴趣。

研究组在此介绍了一类新的Ir（III）钳形配合物，它在空间和电子性质上都表现出优异的模块化和可调性。它们已被证明是C(sp³)-H酰胺化的高效预催化剂（负载低至0.01 mol %），能够合成富集对映体的γ-内酰胺和八氢吲哚衍生物。通过强酸、强碱处理以及加热和催化剂回收实验，研究组证实了这些铱配合物具有显著的稳定性。构效关系研究为推动这些Ir（III）配合物成功的潜在机制提供了有价值的见解。

附：英文原文

Title: Ir(III) Pincer Complex with Solo Coordinatively Active Site as a Surrogate for Half-Sandwich Catalysts: Enabling Asymmetric Acylnitrenoid Transfer and Structure–Activity Relationship Studies

Author: Yun-Peng Chu, Zhen-Hui Xu, Jing Zhao, Chuanyong Wang, Constantin G. Daniliuc, Jiajia Ma

Issue&Volume: October 13, 2025

Abstract: Metal-acylnitrenoid-enabled asymmetric C(sp3)–H amidation has emerged as a highly effective synthetic strategy for accessing enantioenriched amides and chiral amines. While state-of-the-art transition metal catalysts typically feature a half-sandwich scaffold, the exploration of novel catalyst scaffolds remains intriguing. We herein introduce a new class of Ir(III) pincer complexes, which exhibit exceptional modularity and tunability in both steric and electronic properties. They have been demonstrated to function as highly efficient precatalysts (with loadings as low as 0.01 mol %) for C(sp3)–H amidation, enabling the synthesis of enantioenriched γ-lactams and octahydroindole derivatives. The remarkable robustness of these iridium complexes has been confirmed through treatments with strong acid and base, as well as heating and catalyst recovery experiments. Structure–activity relationship studies provided valuable insights into the underlying mechanisms driving the success of these Ir(III) complexes.

DOI: 10.1021/jacs.5c12730

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c12730